Organic light emitting diodes (OLEDs) are attractive due to their potential use in a wide range of lightings as well as high and low resolution display applications. The simplest OLED device contains an organic emission layer sandwiched between two electrodes that inject electrons and holes. The electrons and holes meet in the organic emission layer and produce light. Multiple layers between the two electrodes can make the light production more efficient (Tang et al. (1987) Applied Physics Letters 51: 913-915, and Burroughs et al. (1990) Nature 347: 539). The multiple layers may include one or more electron transport layers, and one or more hole transport layers. See Adachi et al. (1988) Japanese Journal of Applied Physics 27: L269-L271, and Mitschke and Bxc3xa4uerle (2000) J. Mater. Chem. 10: 1471-1507.
This invention relates to compounds useful as a hole transport material in an OLED device.
In one aspect, the present invention features a fluorene compound having the formula: 
Each of R1-R4, R5-R8, and R5-R8, independently, is H, halogen, CN, NO2, amino, alkylamino, arylamino, dialkylamino, diarylamino, hydroxyl, alkoxyl, aryloxyl, heteroaryloxyl, mercapto, alkylthio, arylthio, heteroarylthio, alkyl, aryl, heteroaryl, or heterocyclyl; each of A and B, independently, is phenyl, naphthyl, or phenanthryl; and each of R9 and R10, independently, is H, aryl, heteroaryl, aryloxyl, or heteroaryloxyl; provided that if both A and B are phenyl, then one of R9 and R10 is not H. Note that if each of R5-R8 is the same as each of R5xe2x80x2-R8xe2x80x2, correspondingly, the compounds of this invention are symmetrical. Further, R9 or R10 can be substituted at any suitable position on ring B or A. A subset of the compounds encompassed by the above formula are featured by that each of R9 and R10, independently, is H, aryl, or heteroaryl. In these compounds, each of A and B, independently, can be phenyl or naphthyl, and each of R1-R4, R5-R8, and R5xe2x80x2-R8xe2x80x2, independently, is H, dialkylamino, diarylamino, alkyl, aryl, or heteroaryl.
Alkylamino, arylamino, dialkylamino, diarylamino, alkoxyl, aryloxyl, heteroaryloxyl, alkylthio, arylthio, heteroarylthio, alkyl, aryl, heteroaryl, heterocyclyl, phenyl, naphthyl, and phenanthryl mentioned above include both substituted and unsubstituted moieties. The term xe2x80x9csubstitutedxe2x80x9d refers to one or more substituents (which may be the same or different), each replacing a hydrogen atom. Examples of substituents include, but are not limited to, halogen, amino, alkylamino, arylamino, dialkylamino, diarylamino, hydroxyl, mercapto, cyano, nitro, C1xcx9cC6 alkyl, C1xcx9cC6 alkenyl, C1xcx9cC6 alkoxy, aryl, heteroaryl, or heterocyclyl, wherein alkyl, alkenyl, alkoxy, aryl, heteroaryl, and heterocyclyl are optionally substituted with C1xcx9cC6 alkyl, halogen, amino, alkylamino, arylamino, dialkylamino, diarylamino, hydroxyl, mercapto, cyano, or nitro. The term xe2x80x9carylxe2x80x9d refers to a hydrocarbon ring system having at least one aromatic ring. Examples of aryl moieties include, but are not limited to, phenyl, naphthyl, and pyrenyl. The term xe2x80x9cheteroarylxe2x80x9d refers to a hydrocarbon ring system having at least one aromatic ring which contains at least one heteroatom such as O, N, or S. Examples of heteroaryl moieties include, but are not limited to, pyridinyl, carbazolyl, and indolyl.
One exemplary compound of this invention is 9,9-bis{4-[di-(p-biphenyl)aminophenyl]}fluorene (BPAPF): 
Also within the scope of this invention is an electro-luminescence device made with one or more of the fluorene compounds described above. The device includes an anode layer; a hole transport layer that can include the fluorene compounds of this invention; an electron transport layer; and a cathode layer. The anode, the hole transport layer, the electron transport layer, and the cathode are disposed in the above order.
The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.
This invention relates to fluorene compounds and their use as a hole transport material in an electro-luminescence device.
The fluorene compounds of this invention can be prepared by methods well known to a skilled person in the art, including the synthetic routes disclosed herein.
For example, shown below is a scheme that depicts synthesis of a symmetrical compound (right) and an asymmetrical compound (left) from a starting material such as fluorenone: 
More specifically, a symmetrical compound can be synthesized by the following method: A mixture containing a fluorenone and an aniline is refluxed in the presence of an acid catalyst to produce an intermediate 9,9-bis(aminophenyl)fluorene. The intermediate is subsequently reacted with aryl halides (Arxe2x80x94X and Arxe2x80x2xe2x80x94X, stepwise) in the presence of a catalyst such as palladium to obtain the desired symmetrical product. An asymmetrical compound, on the other hand, can be synthesized as follows: A reaction mixture containing a fluorenone and two different anilines (e.g., an aniline and a 2-fluoroaniline as shown in the above scheme) is refluxed in the presence an acid catalyst to produce a mixture including an asymmetric fluorene intermediate. The asymmetric fluorene intermediate is then reacted with aryl halides (Arxe2x80x94X and Arxe2x80x2xe2x80x94X, stepwise) in the presence of a catalyst such as palladium to produce the desired asymmetrical product.
As another example, a scheme below depicts synthesis of other compounds of this invention from a different starting material such as a dinitro-substituted fluorenone: 
2,7-Bis(diarylamino)-9,9-bis(diarylaminophenyl)fluorene, a compound of this invention, can be synthesized according to the above synthetic route as follows: A mixture of a 2,7-dinitrofluorenone and an aniline is refluxed in the presence of an acid catalyst to give an intermediate 2,7-dinitro-9,9-bis(aminophenyl)fluorene. The two nitro groups are then converted to two amino groups by a reduction reaction with Fe/NH4Cl. Finally, the reduced intermediate is reacted with aryl halides (Arxe2x80x94X and Arxe2x80x2xe2x80x94X, stepwise) in the presence of a catalyst such as palladium to produce the desired product.
BPAPF can be prepared by the method described above. It can also be prepared as follows: A reaction mixture containing commercially available 9, 9-bis(4-aminophenyl)fluorene and 4-bromobiphenyl in toluene is refluxed for 20 hr in the presence of a catalytic amount of Pd2(dba)3, 1,10-phenanthroline, and potassium hydroxide. After cooling, the reaction mixture is filtered and washed with H2O and ethyl acetate. The solid is collected and purified by sublimation.
The compounds of the invention can be used as a hole transport material in an electro-luminescence device.
Typically, the electro-luminescence device can be classified as a two-layer structured device or a three-layer structured device. A two-layer structured device can include a hole transport layer and an electron transport layer, both of which are sandwiched between a pair of electrodes. The electron transport layer can function as a luminescent layer, which transports electrons and emits lights (Tang et al., (1989) J. Appl. Phys. 65: 3610). Generally, a hole transport layer, an electron transport layer, and a cathode layer are deposited sequentially in the above order. The anode layer can be formed on a substrate, such as a glass. A three-layer structured device can include an anode layer, a hole transport layer, a luminescent layer and an electron transport layer, and a cathode layer in the above order. The luminescent layer can be another hole transport or another electron transport layer.
Optionally, the electro-luminescence device can include a dopant-containing layer, which can be an electron transport layer or a luminescent layer. The dopant-containing layer can also be located within the electron transport layer or the luminescent layer, or can be sandwiched between one of the just-mentioned layers and a neighboring layer.
Each of the above mentioned layers can be made of various materials, as described in, for example, U.S. Pat. No. 5,698,740. More specifically, a substrate can be made of, e.g., glass; an anode layer can be a film of a transparent electroconductive material, e.g., indium tin oxide (ITO), formed on the substrate; a hole transport layer can be made of, e.g., 4,4xe2x80x2-bis[N-(1-naphthyl)-N-phenyl-amino]-biphenyl (NPB) or a compound of this invention, formed on the anode layer; an electron transport layer can be made of, e.g., tirs(8-quinolinolate)aluminum (Alq3), deposited on the hole transport layer; and a cathode layer can be made of a metal film, e.g., an alloy of magnesium and silver. The dopant-containing layer can be made of one or more organic fluorescent molecules, e.g., quinacridone.
The fabrication of an electro-luminescence device has been described in, for example, Tang and VanSlyke (1987) Appl. Phys. Lett. 51: 913; Tang et al., (1989) J. Appl. Phys. 65: 3610, or Kido and Lizumi (1997) Chem. Lett. 963. More specifically, each layer may be formed by any one of film forming methods such as vacuum deposition. See U.S. Pat. No. 5,698,740.
Unexpectedly, the compounds of this invention, such as BPAPF, have excellent thermal stability and electrochemical stability, being quantified by parameters such as glass transition temperature (Tg), single oxidation potential (Vo), crystallizing temperature (Tc), or melting temperature (Tm). For example, BPAPF has a Tg of 167xc2x0 C., a Vo of 0.95V, a Tc of 288xc2x0 C., and a Tm of 327xc2x0 C. In contrast, NPB has a Tg of xcx9c100xc2x0 C. and a Vo of 0.83V. See, e.g., O""Brien et al. (1998) Adv. Mater. 10: 1108 or Koene et al. (1998) Adv. Mater. 10: 2235.
The specific examples below are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. Without further elaboration, it is believed that one skilled in the art can, based on the description herein, utilize the present invention to its fullest extent. All publications cited herein are hereby incorporated by reference in their entirety.